title: DFT study of trichloroethene reaction with permanganate in aqueous solution.
abstract: The mechanism of the environmentally important reaction between permanganate anion and trichloroethene (TCE) has been studied theoretically using modern DFT functional. It has been shown that IEFPCM/M05-2X/aug-cc-pVDZ theory level yields activation parameters and carbon isotopic fractionation factor in excellent agreement with the experimental data. Obtained results indicate that this reaction proceeds via the 3+2 mechanism with a very early transition state, in which the new C-O bonds are formed only in about 20%. An alternative, stepwise mechanism that involves initial formation of a single new C-O bond and a C-Mn bond, followed by rearrangement to the permanganate-TCE adduct, has been found to be more energetically demanding and in disagreement with the experimental isotopic fractionation.
authors.affiliation: Institute of Applied Radiation Chemistry, Faculty of Chemistry, Technical University of Lodz , Zeromskiego 116, 90-924 Lodz, Poland.
authors.forename: Paweł
authors.initials: P
authors.lastname: Adamczyk
authors.forename: Agnieszka
authors.initials: A
authors.lastname: Dybala-Defratyka
authors.forename: Piotr
authors.initials: P
authors.lastname: Paneth
mesh_terms: D005591:Chemical Fractionation; D017895:Manganese Compounds / Q000737:chemistry*; D008956:Models, Chemical; D010087:Oxides / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D014241:Trichloroethylene / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000737:chemistry*; D018508:Water Purification
chemical_list: D017895:Manganese Compounds; D010087:Oxides; D012997:Solvents; D014874:Water Pollutants, Chemical; C048856:permanganic acid; D014241:Trichloroethylene